Cleaning solution and semicondcutor process using the same

ABSTRACT

A semiconductor process is provided. First, a metal layer, a dielectric layer and a patterned hard mask layer are sequentially formed on a substrate. Thereafter, a portion of the dielectric layer is removed to form an opening exposing the metal layer. Afterwards, a cleaning solution is used to clean the opening. The cleaning solution includes a triazole compound with a content of 0.00275 to 3 wt %, sulfuric acid with a content of 1 to 10 wt %, hydrofluoric acid with a content of 1 to 200 ppm and water.

BACKGROUND OF THE INVENTION

1. Field of Invention

The present invention relates to a semiconductor process, and more particularly to a cleaning solution and a semiconductor process using the same.

2. Description of Related Art

The dimension of a device is getting smaller as the semiconductor technology is getting developed. When the level of integration of ICs is increased, the surface area of the chip is not sufficient to fabricate the required interconnections in a single layer, so that a design including more than two layers of metal interconnections is adopted in the VLSI technology. The dual damascene process is a widely used metal interconnection technology due to the advantages of improving the device reliability and increasing the production.

The dual damascene process includes forming a dual damascene opening and filling a metal in the dual damascene opening. Generally speaking, a lot of resides form during the process of etching the dual damascene opening. Thus, a cleaning process is performed before the step of filling the metal in the dual damascene opening. Hydrofluoric acid (HF) is usually used as a cleaning solution in the cleaning process. However, when the titanium nitride (TiN) hard mask layer is applied in the dual damascene process, the HF cleaning solution cannot remove the residues effectively and is easy to cause the copper loss in the copper layer exposed by the dual damascene opening; thus, the device feature of the copper layer is affected and the yield of the product is reduced.

SUMMARY OF THE INVENTION

The present invention provides a semiconductor process to prevent the surface of the metal layer exposed by the opening from being corroded by the cleaning solution.

The present invention also provides a cleaning solution, which can clean the opening and prevent the surface of the metal layer exposed by the opening from being corroded.

The present invention provides a semiconductor process. First, a metal layer, a dielectric layer and a patterned hard mask layer are sequentially formed on a substrate. Thereafter, a portion of the dielectric layer is removed to form an opening exposing the metal layer. Afterwards, a cleaning solution is used to clean the opening. The cleaning solution includes a triazole compound with a content of 0.00275 to 3 wt %, sulfuric acid with a content of 1 to 10 wt %, hydrofluoric acid with a content of 1 to 200 ppm and water.

According to an embodiment of the present invention, the triazole compound includes benzotriazole (BTA), for example.

According to an embodiment of the present invention, the metal layer includes a first metal.

According to an embodiment of the present invention, the first meal includes copper, for example.

According to an embodiment of the present invention, the metal layer includes copper or copper alloy, for example.

According to an embodiment of the present invention, the patterned hard mask layer includes a second metal, and the second metal is different from the first metal.

According to an embodiment of the present invention, the second metal includes titanium or tantalum, for example.

According to an embodiment of the present invention, the patterned hard mask layer includes titanium, titanium nitride, tantalum, tantalum nitride or combinations thereof, for example.

According to an embodiment of the present invention, the opening includes a dual damascene opening.

According to an embodiment of the present invention, the opening includes a via opening.

According to an embodiment of the present invention, the dielectric layer includes an inorganic material or an organic material, for example.

According to an embodiment of the present invention, after the step of using the cleaning solution to clean the opening, the process further includes performing another cleaning step by introducing DI water with CO₂.

The present invention also provides a cleaning solution for cleaning an opening in a dielectric layer, wherein the dielectric layer is disposed on a substrate, the opening exposes a metal layer disposed between the dielectric layer and the substrate, and a patterned hard mask layer is disposed on the dielectric layer. The cleaning solution includes a triazole compound with a content of 0.00275 to 3 wt %, sulfuric acid with a content of 1 to 10 wt %, hydrofluoric acid with a content of 1 to 200 ppm and water.

According to an embodiment of the present invention, the triazole compound comprises benzotriazole.

In the present invention, using the cleaning solution including a triazole compound, sulfuric acid, hydrofluoric acid and water to clean the opening can effectively remove the residues generated during the step of forming the opening, especially the polymers formed from the metal-containing hard mask layer. Further, the triazole compound can prevent the metal layer exposed by the opening from being corroded. Thus, the semiconductor process and the cleaning solution of the present invention can reduce the possibility of having an incomplete turning on, a leakage or a short, so that the yield of the product is increased.

In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, a preferred embodiment accompanied with figures is described in detail below.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.

FIGS. 1A to 1F schematically illustrate cross-section views of a semiconductor process according to an embodiment of the present invention.

DESCRIPTION OF EMBODIMENTS

Currently, a metallic material such as titanium nitride (TiN) is used in a hard mask layer in a dual damascene process. However, after the dielectric layer is etched to form a dual damascene opening, the residues include polymers formed from the etching gases, organic polymers formed from the etching gases and the dielectric layer and metal-containing polymers formed from the etching gases and the TiN hard mask layer, so that the conventional HF cleaning solution cannot remove the formed residues effectively.

Further, the dual damascene opening exposes two kinds of the metals, one of which is titanium of the TiN hard mask layer on the sidewall of the dual damascene opening, and the other of which is copper of the copper layer exposed at the bottom of the dual damascene opening. During the cleaning process, the conventional HF cleaning solution has become a good electrolyte, so that the Galvanic effect is generated, the surface of the copper layer is corroded, and the copper loss is caused. On the contrary, the present invention provides a semiconductor process in which the cleaning solution can achieve the purpose of effective cleaning and copper loss is avoided.

In an embodiment of the present invention, the cleaning solution includes a triazole compound with a content of 0.00275 to 3 wt %, sulfuric acid with a content of 1 to 10 wt %, hydrofluoric acid with a content of 1 to 200 ppm and water.

The following dual damascene process is provided for illustration purposes and is not to be construed as limiting the present invention.

FIGS. 1A to 1F schematically illustrate cross-section views of a semiconductor process according to an embodiment of the present invention.

Referring to FIG. 1A, a substrate 100 having a metal layer 102 thereon is provided. The substrate 100 may be a P-type doped silicon substrate, a N-type doped silicon substrate, an epitaxial silicon substrate, a gallium arsenide (GaAs) substrate, an indium phosphide (InP) substrate or a silicon germanium (SiGe) substrate. The metal layer 102 may be a conductive line, such as a copper line, in the interconnection process. In this embodiment, the metal layer 102 includes a copper-containing material such as copper or copper alloy. In an embodiment, the copper alloy may be a copper silicon alloy.

Thereafter, a dielectric layer 104 is formed on the metal layer 102. The dielectric layer 104 may include a low dielectric constant material (dielectric constant k<4). The low k material may be an inorganic material such as hydrogen silsesquioxane (HSQ) or fluorinated silicate glass (FSG), or an organic material such as fluorinated poly-(arylene ether) (Flare), poly-(arylene either) (SILK) or parylene. The method of forming the dielectric layer 104 includes performing a chemical vapor deposition (CVD) process, for example.

Afterwards, a hard mask layer 106 and a photoresist layer 107 having a trench pattern 107 a are sequentially formed on the dielectric layer 104. In an embodiment, the hard mask layer 106 includes a titanium-containing material such as titanium or TiN, a tantalum-containing material such as tantalum or tantalum nitride (TaN), or combinations thereof. The method of forming the hard mask layer 106 includes performing a CVD process or a physical vapor deposition (PVD) process, for example.

Referring to FIG. 1B, an etching process is performed, using the photoresist layer 107 (FIG. 1A) as a mask, to transfer the trench pattern 107 a to a portion of the dielectric layer 104, so as to form an opening 112 in the dielectric layer 104. Thereafter, the photoresist layer 107 is removed. Afterwards, a photoresist layer 108 having a via opening pattern 108 a is formed on the substrate 100. The method of removing the portion of the dielectric layer 104 includes performing a dry etching process, and the etching gases include CHF₃, CF₄, CH₄ and Ar, for example.

Referring to FIG. 1C, a portion of the dielectric layer 104 is removed, using the photoresist layer 108 as a mask, so as to transfer the via opening pattern 108 a to the dielectric layer 104; thus, an opening 110 without exposing the metal layer 102 is formed. The method of removing the portion of the dielectric layer 104 includes performing a dry etching process, and the etching gases include C₄H₈, CF₄, CHF₃, N₂ and Ar, for example.

Referring to FIG. 1D, the photoresist layer 108 is removed. Afterwards, a portion of the dielectric layer 104 is removed, using the patterned hard mask layer 106 a as a mask, so as to form a trench 112 a and a via opening 110 a which exposes the metal layer 102. In this embodiment, the trench 112 a may be an opening for forming a conductive line. The via opening 110 a and the trench 112 a form the opening 114, so that the opening 114 is a dual damascene opening. The method of removing the portion of the dielectric layer 104 includes performing a dry etching process, and the etching gases include CF₄, CO and Ar, for example. During the step of removing the portion of the dielectric layer 104, residues are generated in the opening 114 and on the surface of the patterned hard mask layer 106 a. The residues include organic polymers formed from the etching gases and the dielectric layer 104, and metal-containing polymers formed from the etching gases and the metal of the patterned hard mask layer 106 a. The residues may cause a profile change of the opening 114, an incomplete turning on, a leakage or a short, so that the reliability of the device is reduced. Accordingly, the residues have to be removed completely.

Referring again to FIG. 1D, a cleaning solution C is used to clean the opening 114. The cleaning solution C for removing the polymers generated from the etching process includes a triazole compound with a content of 0.0275 to 3 wt %, sulfuric acid with a content of 1 to 10 wt %, hydrofluoric acid with a content of 1 to 200 ppm and water. The sulfuric acid can effectively remove the polymers formed from the metal-containing hard mask layer. During the cleaning process, the triazole compound forms a protective film on the surface of the metal layer 102 to prevent the metal layer 102 from being corroded. In details, the triazole compound reacts with the surface of the metal layer 102 to form a chelating complex to avoid the metal layer 102 from being in contact with the cleaning solution C. In this embodiment, the triazole compound such as benzotritriazolele (BTA) reacts with the surface copper of the metal layer 102 to form a copper-containing chelating complex. The chelating complex is like a protective film covering the surface of the metal layer 102, so that the metal layer 102 is protected and the Galvanic effect is avoided; in other words, the metal layer 102 is not corroded so that the reliability of the device is enhanced. Therefore, the cleaning solution C can remove the organic polymers and metal-containing polymers formed in the opening 114, and protect the metal layer 102 exposed by the opening 114 from being corroded or damaged during the etching process. After the step of using the cleaning solution C, another cleaning step is performed by introducing de-ionized (DI) water. In an embodiment, during the step of introducing DI water, CO₂ is introduced simultaneously to further prevent loss of the metal layer 102 exposed by the opening 114 in the cleaning process. The introduced amount of CO₂ is the amount which can reduce the water resistance to about 9000-1000 K ohm.

Referring to FIG. 1E, a conductive layer 116 is formed on the substrate 100 to fill the opening 114. In this embodiment, the conductive layer 116 includes a metal layer 118 and a barrier layer 120. The metal layer 118 includes copper or copper alloy. The barrier layer 120 includes TiN or TaN.

Referring to FIG. 1F, the patterned hard mask layer 106 a and a portion of the conductive layer 116 are removed to form a via plug 122 and a conductive line 124. The method of removing the patterned hard mask layer 106 a and the portion of the conductive layer 116 includes performing a chemical mechanical polishing (CMP) process.

This embodiment in which the dual damascene opening is formed by subsequently using the patterned photoresist layer and the patterned hard mask layer as a mask is provided for illustration purposes, and is not to be construed as limiting the present invention. It is appreciated by persons skilled in the art that the dual damascene opening can be formed by other known methods. Further, in another embodiment, the opening can be a contact hole; that is, the opening cleaned by the cleaning solution is not limited by the dual damascene opening of the present invention.

In this embodiment, after the opening is formed, the sulfuric acid in the cleaning solution can remove the polymers formed from the metal-containing hard mask layer, so as to avoid profile change of the opening, incomplete turning on between layers, a leakage or a short. The triazole compound in the cleaning solution can form a chelating complex with the surface of the metal layer exposed by the opening, so as to prevent the metal layer from being corroded or damaged; thus, the reliability of the device is enhanced.

Further, after the step of using the cleaning solution of the present invention, another cleaning step is performed by introducing DI water with CO₂, so as to further prevent loss of the exposed metal layer in the cleaning process.

EXAMPLES

In the following examples, a cleaning process is performed to some tested samples with different cleaning solutions. Each of the tested samples has a copper layer, a dielectric layer and a TiN hard mask layer subsequently formed thereon, and the dielectric layer has an opening exposing the copper layer.

Example 1

In example 1, a cleaning process is performed to the tested samples respectively with a cleaning solution only including HF and another cleaning solution including HF and sulfuric acid. The results show that the tested sample has a lot of residues remained thereon after cleaned by the cleaning solution only including HF, while the tested sample has no residue remained thereon after cleaned by the cleaning solution including HF and sulfuric acid. The better polymer cleaning performance with the cleaning solution including HF and sulfuric acid indicates that the sulfuric acid can effectively remove the residues formed from the TiN hard mask layer. Further, the content of the sulfuric acid in the cleaning solution is between 1 wt % and 10 wt %. The cleaning performance is not good enough when the content of the sulfuric acid in the cleaning solution is less than 1 wt %. The copper layer is corroded when the content of the sulfuric acid in the cleaning solution is more than 10 wt %.

Example 2

A cleaning process is performed to the tested samples with the cleaning solutions as shown in Table 1 including HF, sulfuric acid and different concentrations of BTA. Each of the tested samples is observed for the recess depth of the copper layer after cleaning. The recess degree is calculated by the standard of the recess depth of the copper layer of the tested sample with the cleaning solution 1 (shown as 100% in Table 1). The concentration of the sulfuric acid in the cleaning solutions 1 to 4 is 5 wt %. The concentration of the HF in the cleaning solution is 20 ppm.

TABLE 1 BTA Recess Cleaning concentration depth Recess degree solution (wt %) (nm) (%) 1    0% 43.7 100 2 0.00275%  17.5 40.05 3 0.0055% 16.6 37.99 4 0.0275% 12.4 28.36

As shown in Table 1, using the cleaning solutions 2 to 4 including BTA to clean the tested samples can significantly reduce the recess degree of the copper layer etched by the cleaning solution. Thus, the BTA in the cleaning solution can prevent the copper layer exposed by the opening from being etched by the cleaning solution. Further, the BTA concentration is related to the recess degree of the copper layer of the tested sample.

Example 3

In example 3, a cleaning process is performed to the tested samples with the cleaning solutions as shown in Table 2 including HF, sulfuric acid and different concentrations of BTA. Each of the tested samples is measured for the resistance of the copper layer after cleaning, and the degree of corrosion is compared according to the resistance of the copper layer. In other words, the higher resistance of the copper layer, the higher degree of corrosion of the copper layer etched by the cleaning solution. The concentration of the sulfuric acid in the cleaning solutions 1 to 4 is 5 wt %. The concentration of the HF in the cleaning solution is 20 ppm.

TABLE 2 Resistance Average Volume ratio distribution resistance Cleaning of cleaning of copper of copper solution solution to BTA layer (OHM) layer (OHM) 1 No BTA   8~13.5 9.98 2 100:1 4~6 5.42 3 100:2 4~6 5.27 4  100:10 4~6 5.15

As shown in Table 2, using the cleaning solutions 2 to 4 including BTA to clean the tested samples can effectively reduce the degree of corrosion of the copper layer etched by the cleaning solution. Further, compared to the cleaning solution 1 without BTA, the cleaning solutions 2 to 4 including BTA can significantly reduce the resistance distribution. That is, the BTA in the cleaning solution is capable of preventing the copper layer exposed by the opening from being corroded by the cleaning solution.

In summary, the semiconductor process and the cleaning solution of the present invention can effectively remove the residues generated in the opening, especially the polymers formed from the metal-containing hard mask layer, so that the profile of the opening can be kept. Further, the triazole compound in the cleaning solution can form a chelating complex with the surface of the metal layer exposed by the opening, so as to prevent the metal layer from being in contact with the cleaning solution and enhance the conductivity characteristics of the device. Thus, the semiconductor process and the cleaning solution of the present invention can reduce the possibility of having an incomplete turning on, a leakage or a short, so that that yield of the product is increased.

This invention has been disclosed above in the preferred embodiments, but is not limited to those. It is known to persons skilled in the art that some modifications and innovations may be made without departing from the spirit and scope of this invention. Hence, the scope of this invention should be defined by the following claims. 

1. A semiconductor process, comprising: forming a metal layer, a dielectric layer and a patterned hard mask layer sequentially on a substrate; removing a portion of the dielectric layer to form an opening exposing the metal layer; and using a cleaning solution to clean the opening, the cleaning solution comprising: a triazole compound with a content of 0.00275 to 3 wt %; sulfuric acid with a content of 1 to 10 wt %: hydrofluoric acid with a content of 1 to 200 ppm; and water.
 2. The process of claim 1, wherein the triazole compound comprises benzotriazole.
 3. The process of claim 1, wherein the metal layer comprises a first metal.
 4. The process of claim 3, the first meal comprises copper.
 5. The process of claim 4, wherein the metal layer comprises copper or copper alloy.
 6. The process of claim 3, wherein the patterned hard mask layer comprises a second metal, and the second metal is different from the first metal.
 7. The process of claim 6, wherein the second metal comprises titanium or tantalum.
 8. The process of claim 7, wherein the patterned hard mask layer comprises titanium, titanium nitride, tantalum, tantalum nitride or combinations thereof.
 9. The process of claim 1, wherein the opening comprises a dual damascene opening.
 10. The process of claim 1, wherein the opening comprises a via opening.
 11. The process of claim 1, wherein the dielectric layer comprises an inorganic material or an organic material.
 12. The process of claim 1, further comprising performing another cleaning step by introducing DI water with CO₂ after the step of using the cleaning solution to clean the opening.
 13. A cleaning solution for cleaning an opening in a dielectric layer, wherein the dielectric layer is disposed on a substrate, the opening exposes a metal layer disposed between the dielectric layer and the substrate, and a patterned hard mask layer is disposed on the dielectric layer, comprising: a triazole compound with a content of 0.00275 to 3 wt %; sulfuric acid with a content of 1 to 10 wt %; hydrofluoric acid with a content of 1 to 200 ppm; and water.
 14. The cleaning solution of claim 13, wherein the triazole compound comprises benzotriazole. 